Polycyclic fused heteroring compounds metal complexes and polymerization process

ABSTRACT

Metal complexes comprising a polycyclic, heteroatom containing fused ring compound comprising at least a cyclopentadienyl ring having fused thereto a 5-membered polyatomic ring containing one or more ring atoms selected from groups 15 or 16 of the Periodic Table of the Elements and lacking substituents forming 6-membered, aromatic fused rings; polymerization catalysts; and olefin polymerization processes using the same are disclosed.

CROSS REFERENCE STATEMENT

For purposes of United States patent practice, this application claimsthe benefit of U.S. Provisional Application No. 60/364,809, filed Mar.14, 2002.

BACKGROUND OF THE INVENTION

This invention relates to a class of metal complexes containing apolycyclic, fused ring ligand containing one or more Group 15 or 16atoms, and to polymerization catalysts derived from such complexes thatare particularly suitable for use in a polymerization process forpreparing homopolymers and copolymers of olefins or diolefins, includingcopolymers comprising two or more olefins or diolefins such ascopolymers comprising an α-olefin and ethylene or a monovinyl aromaticmonomer and ethylene.

Constrained geometry metal complexes and methods for their preparationare disclosed in U.S. Pat. No. 5,703,187. This publication also teachesthe preparation of certain novel copolymers of ethylene and a hinderedvinyl monomer, including monovinyl aromatic monomers, having apseudo-random incorporation of the hindered vinyl monomer therein.Additional teachings of constrained geometry catalysts may be found inU.S. Pat. Nos. 5,321,106, 5,721,185, 5,374,696, 5,470,993, 5,541,349,and 5,486,632, as well as WO97/15583, and WO97/19463.

Certain highly active, polycyclic aromatic, metal complexes, especiallyderivatives of s-indacenyl or cyclopentaphenanthrenyl ligand groups aredisclosed in U.S. Pat. Nos. 6,034,022 and 6,329,486. Additionalcomplexes based on non-aromatic polycyclic ring systems were disclosedin Ser. No. 09/879,463, filed Jun. 12, 2001, published asUS-A-2002/0062011, on May 23, 2002. Metallocenes with heteroatomcontaining delocalized fused ring systems are disclosed in WO01/53360,WO01/44318, WO01/47939, WO01/48039, WO01/48040, WO98/06728 and U.S. Pat.No. 6,268,444, and suggested in U.S. Ser. No. 10/124,269, published asUS-A-2002/0151662, on Oct. 17, 2002.

Despite the advance in the art obtained by the foregoing metalcomplexes, catalysts possessing improved catalytic performance are stilldesired by the industry. In particular, it would be desirable to provideimproved metal complexes that may be readily synthesized. Accordingly,it would be desirable if there were provided metal complexes having goodcatalytic properties combined with relative ease of synthesis.

SUMMARY OF THE INVENTION

According to the present invention there is provided a polycyclic,heteroatom containing fused ring compound corresponding to the formula:CpM(Z)(X)_(x)(T)_(t)(X′)_(x′) (I),

-   -   where Cp is a polycyclic, fused ring ligand or inertly        substituted derivative thereof having up to 60 atoms not        counting hydrogen, said Cp comprising at least a        cyclopentadienyl ring bound to M by means of delocalized        π-electrons and having fused thereto a 5-membered polyatomic        ring containing one or more ring atoms selected from groups 15        or 16 of the Periodic Table of the Elements, or substituted        derivatives thereof, with the proviso that said cyclopentadienyl        ring lacks adjacent substituents that together form a second        fused ring;    -   M is a metal selected from Groups 3-10 or the Lanthanide series        of the Periodic Table of the Elements;    -   Z is a divalent moiety of the formula -Z′Y— joining Cp and M,        wherein,    -   Z′ is SiR⁶ ₂, CR⁶ ₂, SiR⁶ ₂SiR⁶ ₂, CR⁶ ₂CR⁶ ₂, CR⁶═CR⁶, CR⁶        ₂SiR⁶ ₂, BR⁶, or GeR⁶ ₂;    -   Y is —O—, —S—, —NR⁵—, —PR⁵—; —NR⁵ ₂, or —PR⁵ ₂;    -   R⁵, independently each occurrence, is hydrocarbyl,        trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl, said R⁵        having up to 20 atoms other than hydrogen, and optionally two R⁵        groups or R⁵ together with Y form a ring system;    -   R⁶, independently each occurrence, is hydrogen, or a member        selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated        alkyl, halogenated aryl, —NR⁵ ₂, and combinations thereof, said        R⁶ having up to 30 non-hydrogen atoms, and optionally, two R⁶        groups form a ring system;    -   X is hydrogen or a monovalent anionic ligand group having up to        60 atoms not counting hydrogen;    -   T independently each occurrence is a neutral ligating compound        having up to 20 atoms, other than hydrogen, and optionally T and        X or T and R⁵ are bonded together;    -   X′ is a divalent anionic ligand group having up to 60 atoms        other than hydrogen;    -   x is 0, 1, 2, or 3;    -   t is a number from 0 to 2, and    -   x′ is 0 or 1.

The above compounds may exist as isolated crystals, as a mixture withother compounds, in the form of a solvated adduct, dissolved in asolvent, especially an organic liquid solvent, in the form of a dimer,or as a chelated derivative, especially wherein the chelating agent isan organic material such as ethylenediaminetetraacetic acid (EDTA).

Also, according to the present invention, there is provided a catalystfor olefin polymerization comprising:

-   A. i) a metal compound of formula (I), and-    ii) an activating cocatalyst,    the molar ratio of i) to ii) being from 1:10,000 to 100:1, or-   B. the reaction product formed by converting a metal compound of    formula (I) to an active catalyst by use of an activating technique.

Further according to the present invention there is provided a processfor the polymerization of olefins comprising contacting one or moreC₂₋₂₀ olefins, including cyclic olefins, under polymerization conditionswith a catalyst comprising:

-   A. i) a metal compound of formula (I), and-    ii) an activating cocatalyst,    the molar ratio of i) to ii) being from 1:10,000 to 100:1, or-   B. the reaction product formed by converting a metal compound of    formula (II) to an active catalyst by use of an activating    technique.

The present catalysts and polymerization processes are especiallyefficient for production of olefin homopolymers, copolymers of two ormore olefins, in particular, copolymers of ethylene and a C₃₋₈ α-olefinor a vinylaromatic monomer, such as styrene, and interpolymers of threeor more such polymerizable monomers over a wide range of polymerizationconditions, and especially at elevated temperatures. They are especiallyuseful for the formation of ethylene homopolymers and copolymers ofethylene and one or more C₃₋₈ α-olefins as well as copolymers ofethylene, propylene and a diene (EPDM copolymers). Examples of suitablediene monomers include ethylidenenorbornene, 1,4-hexadiene or similarconjugated or nonconjugated dienes.

The catalysts of this invention may also be supported on a solidmaterial and used in olefin polymerization processes in a slurry or inthe gas phase. The catalyst may be prepolymerized with one or moreolefin monomers in situ in a polymerization reactor or in a separateprocess with intermediate recovery of the prepolymerized catalyst priorto the primary polymerization process. They may also be combined withone or more additional catalysts whether metallocene or conventionalZiegler-Natta catalysts and used together or sequentially in one or morethan one polymerization reactors according to the present process. Inaddition to their use as polymerization catalysts, compounds accordingto the present invention may be used for hydroformulation, hydrogenationor oligomerization processes.

DETAILED DESCRIPTION OF THE INVENTION

All reference to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 1995. Also, any reference to a Group or Groups shall be tothe Group or Groups as reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups. For purposes of UnitedStates patent practice, the contents of any patent, patent applicationor publication referenced herein is hereby incorporated by reference inits entirety herein, especially with respect to its disclosure oforganometallic structures, synthetic techniques and general knowledge inthe art. As used herein the term “aromatic” refers to a polyatomic,cyclic, ring system containing (4δ+2) π-electrons, wherein δ is aninteger greater than or equal to 1. The term “fused” as used herein withrespect to a ring system containing two or more polyatomic, cyclic ringsmeans that with respect to at least two rings thereof, at least one pairof adjacent atoms is included in both rings.

If appearing herein, the term “comprising” and derivatives thereof isnot intended to exclude the presence of any additional component, stepor procedure, whether or not the same is disclosed herein. In order toavoid any doubt, all compositions claimed herein through use of the term“comprising” may include any additional additive, adjuvant, or compound,unless stated to the contrary. In contrast, the term, “consistingessentially of” if appearing herein, excludes from the scope of anysucceeding recitation any other component, step or procedure, exceptingthose that are not essential to operability. The term “consisting of”,if used, excludes any component, step or procedure not specificallydelineated or listed. The term “or”, unless stated otherwise, refers tothe listed members individually as well as in any combination.

Desirably, the compounds of the invention contain a cyclopentadienylring fused to a 5-membered ring at positions adjacent to one or morenitrogen, sulfur or oxygen heteroatoms contained in said 5-memberedring.

Preferred compounds (metal complexes) of the invention are thosecorresponding to the formula:

wherein:

-   -   J independently each occurrence is hydrogen, hydrocarbyl,        trihydrocarbylsilyl, trihydrocarbylgermyl, halide,        hydrocarbyloxy, trihydrocarbylsiloxy,        bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino,        hydrocarbyleneamino, hydrocarbylimino, di(hydrocarbyl)phosphino,        hydrocarbylenephosphino, hydrocarbylsulfido, halo-substituted        hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,        trihydrocarbylsilyl-substituted hydrocarbyl,        trihydrocarbylsiloxy-substituted hydrocarbyl,        bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,        di(hydrocarbyl)amino-substituted hydrocarbyl,        hydrocarbyleneamino-substituted hydrocarbyl,        di(hydrocarbyl)phosphino-substituted hydrocarbyl,        hydrocarbylenephosphino-substituted hydrocarbyl, or        hydrocarbylsulfido-substituted hydrocarbyl, said J group having        up to 40 atoms not counting hydrogen atoms;    -   A is the divalent remnant of a 5-membered, aromatic ring group        or substituted derivatives thereof, including polycyclic fused        ring derivatives thereof, said A containing at least one Group        15 or 16 ring atom, preferably nitrogen, sulfur or oxygen, most        preferably nitrogen; and    -   M is a Group 4 metal;    -   Y is —O—, —S—, —NR⁵—, —PR⁵—; —NR⁵ ₂, or —PR⁵ ₂;    -   Z′ is SiR⁶ ₂, CR⁶ ₂, SiR⁶ ₂SiR⁶ ₂, CR⁶ ₂CR⁶ ₂, CR⁶═CR⁶, CR⁶        ₂SiR⁶ ₂, BR⁶, or GeR⁶ ₂;    -   R⁵ each occurrence is independently hydrocarbyl,        trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl, said R⁵        having up to 20 atoms other than hydrogen, and optionally two R⁵        groups or R⁵ together with Y form a ring system;    -   R⁶ each occurrence is independently hydrogen, or a member        selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated        alkyl, halogenated aryl, —NR⁵ ₂, and combinations thereof, said        R⁶ having up to 20 non-hydrogen atoms, and optionally, two R⁶        groups form a ring system;    -   X, T, and X′ are as previously defined;    -   x is 0, 1 or 2;    -   t is 0 or 1; and    -   x′is 0 or 1.

In a desirable embodiment, when x is 2, x′ is zero, M is in the +4formal oxidation state (or M is in the +3 formal oxidation state if Y is—NR⁵ ₂ or —PR⁵ ₂), and X is an anionic ligand selected from the groupconsisting of halide, hydrocarbyl, hydrocarbyloxy, di(hydrocarbyl)amido,di(hydrocarbyl)phosphido, hydrocarbylsulfido, and silyl groups, as wellas halo-, di(hydrocarbyl)amino-, hydrocarbyloxy-, anddi(hydrocarbyl)phosphino-substituted derivatives thereof, said X grouphaving up to 30 atoms not counting hydrogen,

-   -   when x is 0 and x′ is 1, M is in the +4 formal oxidation state,        and X′ is a dianionic ligand selected from the group consisting        of hydrocarbadiyl, oxyhydrocarbylene, silane, and        hydrocarbylenedioxy groups, said X group having up to 30        nonhydrogen atoms,    -   when x is 1, and x′ is 0, M is in the +3 formal oxidation state,        and X is a stabilizing anionic ligand group selected from the        group consisting of allyl, 2-(N,N-dimethylamino)phenyl,        2-(N,N-dimethylaminomethyl)phenyl, and        2-(N,N-dimethylamino)benzyl, and    -   when x and x′ are both 0, 1 is 1, M is in the +2 formal        oxidation state, and T is a neutral, conjugated or nonconjugated        diene, optionally substituted with one or more hydrocarbyl        groups, said T having up to 40 carbon atoms and being bound to M        by means of delocalized π-electrons thereof.

In the metal complexes, preferred T groups are carbon monoxide;phosphines, especially trimethylphosphine, triethylphosphine,triphenylphosphine and bis(1,2-dimethylphosphino)ethane; P(OR⁴)₃,wherein R⁴ is C₁₋₂₀ hydrocarbyl; ethers, especially tetrahydrofuran;amines, especially pyridine, bipyridine, tetramethylethylenediamine(TMEDA), and triethylamine; olefins; and neutral conjugated dieneshaving from 4 to 40, preferably 5 to 40 carbon atoms. Complexesincluding neutral diene T groups are those wherein the metal is in the+2 formal oxidation state.

Further in reference to the metal complexes, X preferably is desirablyselected from the group consisting of hydro, halo, hydrocarbyl, silyl,and N,N-dialkylamino-substituted hydrocarbyl. The number of X groupsdepends on the oxidation state of M, whether Z is divalent or not andwhether any neutral diene groups or divalent X′ groups are present. Theskilled artisan will appreciate that the quantity of the varioussubstituents and the identity of Z are chosen to provide charge balance,thereby resulting in a neutral metal complex. For example, when Z isdivalent, and x is zero, x′ is two less than the formal oxidation stateof M. When Z contains one neutral two electron coordinate-covalentbonding site, and M is in a formal oxidation state of +3, x may equalzero and x′ equal 1, or x may equal 2 and x′ equal zero. In a finalexample, if M is in a formal oxidation state of +2, Z may be a divalentligand group, whereupon x and x′ are both equal to zero and one neutralT ligand group may be present.

Highly preferred compounds of formula (I) are those wherein M istitanium.

Examples of suitable A moieties may be depicted graphically as follows:

More highly preferred compounds and metal complexes of formula (I)according to the present invention correspond to the formula:

-   -   wherein    -   M is titanium;    -   R¹ each occurrence is hydrogen or a hydrocarbyl, hydrocarbyloxy,        dihydrocarbylamino, hydrocarbyleneamino,        dihydrocarbylamino-substituted hydrocarbyl group, or        hydrocarbyleneamino-substituted hydrocarbyl group of up to 30        atoms not counting hydrogen, and optionally two R¹ groups may be        joined together;    -   Y is —O—, —S—, —NR⁵—, —PR⁵—; —NR⁵ ₂, or —PR⁵ ₂;    -   Z′ is SiR⁶ ₂, CR⁶ ₂, SiR⁶ ₂SiR⁶ ₂, CR⁶ ₂CR⁶ ₂, CR⁶═CR⁶, CR⁶        ₂SiR⁶ ₂, BR⁶, or GeR⁶ ₂;    -   R⁵ each occurrence is independently hydrocarbyl,        trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl, said R⁵        having up to 20 atoms other than hydrogen, and optionally two R⁵        groups or R⁵ together with Y form a ring system;    -   R⁶ each occurrence is independently hydrogen, or a member        selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated        alkyl, halogenated aryl, —NR⁵ ₂, and combinations thereof, said        R⁶ having up to 20 non-hydrogen atoms, and optionally, two R⁶        groups form a ring system;    -   X, T, and X′ are as previously defined;    -   x is 0, or 2;    -   t is 0 or 1; and

-   x′ is 0 or 1;    -   and, when x is 2, x′ is zero, M is in the +4 formal oxidation        state (or M is in the +3 formal oxidation state if Y is —NR⁵ ₂        or —PR⁵ ₂), and X is an anionic ligand selected from the group        consisting of halide, hydrocarbyl, hydrocarbyloxy,        di(hydrocarbyl)amido, di(hydrocarbyl)phosphido,        hydrocarbylsulfido, and silyl groups, as well as halo-,        di(hydrocarbyl)amino-, hydrocarbyloxy-, and        di(hydrocarbyl)phosphino-substituted derivatives thereof, said X        group having up to 30 atoms not counting hydrogen,    -   when x is 0 and x′ is 1, M is in the +4 formal oxidation state,        and X′ is a dianionic ligand selected from the group consisting        of hydrocarbadiyl, silane, oxyhydrocarbylene, and        hydrocarbylenedioxy groups, said X group having up to 30        nonhydrogen atoms,    -   when x is 1, and x′ is 0, M is in the +3 formal oxidation state,        and X is a stabilizing anionic ligand group selected from the        group consisting of allyl, 2-(N,N-dimethylamino)phenyl,        2-(N,N-dimethylaminomethyl)phenyl, and        2-(N,N-dimethylamino)benzyl, and    -   when x and x′ are both 0, t is 1, M is in the +2 formal        oxidation state, and T is a neutral, conjugated or nonconjugated        diene, optionally substituted with one or more hydrocarbyl        groups, said T having up to 40 carbon atoms and being bound to M        by means of delocalized π-electrons thereof.

Most highly preferably, R¹ each occurrence is hydrogen,

-   -   Y is NR⁵ wherein R⁵ is C₁₋₁₀ alkyl or cycloalkyl, preferably        t-butyl; and    -   Z′ is dimethylsilane;    -   and, when x is 2, t and x′ are both zero, M is in the +4 formal        oxidation state, and X is independently each occurrence methyl,        benzyl, or halide;    -   when x and t are zero, x′ is one, and M is in the +4 formal        oxidation state, X′ is —CH₂Si(CH₃)₂CH₂— or a 1,4-butenediyl        group that forms a metallocyclopentene ring with M,    -   when x is 1, t and x′ are zero, M is in the +3 formal oxidation        state, and X is 2-(N,N-dimethylamino)benzyl; and    -   when x and x′ are 0, t is 1, M is in the +2 formal oxidation        state, and T is 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene.

Most preferred metal complexes according to formula (I) according to theinvention are compounds corresponding to the following formulas:

wherein R¹ is C₁₋₃₀ hydrocarbyl, preferably methyl, or a C₄₋₃₀ alkyl oraralkyl group containing a secondary or tertiary substitution pattern atthe β-carbon thereof, most preferably methyl, 2,2-dimethylpropan-1-yl,2,2-dimethylbutan-1-yl, 2,2-diethylpropan-1-yl, 2,2-diethylbutan-1-yl,benzyl or pentafluorophenylmethyl group.

The metal complexes can be prepared by combining a metal halide saltwith the corresponding fused, polycyclic ring system ligand dianion inan inert diluent, or by combining a metal amide with the correspondingneutral fused, polycyclic ring system in an inert diluent. Optionally areducing agent can be employed to produce the lower oxidation statecomplexes, and standard ligand exchange procedures can by used toproduce different ligand substituents. Processes that are suitablyadapted for use herein are well known to synthetic organometallicchemists. The syntheses are preferably conducted in a suitablenoninterfering solvent at a temperature from −100 to 300° C., preferablyfrom −78 to 100° C., most preferably from 0 to 50° C. By the term“reducing agent” herein is meant a metal or compound which, underreducing conditions causes the metal M, to be reduced from a higher to alower oxidation state. Examples of suitable metal reducing agents arealkali metals, alkaline earth metals, aluminum and zinc, alloys ofalkali metals or alkaline earth metals such as sodium/mercury amalgamand sodium/potassium alloy. Examples of suitable reducing agentcompounds are sodium naphthalenide, potassium graphite, lithium alkyls,lithium or potassium alkadienyls; and Grignard reagents. Most preferredreducing agents are the alkali metals or alkaline earth metals,especially lithium and magnesium metal.

Suitable reaction media for the formation of the complexes includealiphatic and aromatic hydrocarbons, ethers, and cyclic ethers,particularly branched-chain hydrocarbons such as isobutane, butane,pentane, hexane, heptane, octane, and mixtures thereof; cyclic andalicyclic hydrocarbons such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof; aromaticand hydrocarbyl-substituted aromatic compounds such as benzene, toluene,and xylene, C₁₋₄ dialkyl ethers, C₁₋₄ dialkyl ether derivatives of(poly)alkylene glycols, and tetrahydrofuran. Mixtures of the foregoingare also suitable.

Illustrative metal complexes according to the present invention include:

-   [1-[(3a,4,5,6,6a-η)-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato    (2-)-κN]dichloro titanium),-   [1-[(3a,4,5,6,6a-η)-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato    (2-)-κN]dimethyl titanium),-   [1-[(3a,4,5,6,6a-η)-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato    (2-)-κN]dibenzyl titanium),-   [1-[(3a,4,5,6,6a-η)-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato    (2-)-κN]titanium (II) 1,3-pentadiene),-   [1-[(3a,4,5,6,6a-η)-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato    (2-)-κN]titanium (II) 1,4-diphenyl-1,3-butadiene,-   [1-[(3a,4,5,6,6a-η)-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato    (2)-κN]titanium (III) 2-(N,N-dimethylamino)benzyl),-   [1-[(3a,4,5,6,6a-η)-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dichloro    titanium),-   [1-[(3a,4,5,6,6a-η)-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dimethyl    titanium),-   [1-[(3a,4,5,6,6a-η)-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dibenzyl    titanium),-   [1-[(3a,4,5,6,6a-η)-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (II)    1,3-pentadiene),-   [1-[(3a,4,5,6,6a-η)-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (II)    1,4-diphenyl-1,3-butadiene,-   [1-[(3a,4,5,6,6a-η)-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (II)    2-(N,N-dimethylamino)benzyl),-   [1-[(3a,4,5,6,6a-η)-3-phenyl-5-methyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dichloro    titanium),-   [1-[(3a,4,5,6,6a-η)-3-phenyl-5-methyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dimethyl    titanium),-   [1-[(3a,4,5,6,6a-η)-3-phenyl-5-methyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dibenzyl    titanium),-   [1-[(3a,4,5,6,6a-ηi)-3-phenyl-5-methyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (II)    1,3-pentadiene),-   [1-[(3a,4,5,6,6a-η)-3-phenyl-5-methyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (II)    1,4-diphenyl-1,3-butadiene,-   [1-[(3a,4,5,6,6a-η)-3-phenyl-5-methyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (III)    2-(N,N-diethylamino)benzyl),-   [1-[(3a,4,5,6,6a-η)-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dichloro    titanium),-   [1-[(3a,4,5,6,6a-η)-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dimethyl    titanium),-   [1-[(3a,4,5,6,6a-η)-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dibenzyl    titanium),-   [1-[(3a,4,5,6,6a-η)-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (II)    1,3-pentadiene),-   [1-[(3a,4,5,6,6a-η)-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (II)    1,4-diphenyl-1,3-butadiene,-   [1-[(3a,4,5,6,6a-η)-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (III)    2-(N,N-dimethylamino)benzyl),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-cyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dichloro    titanium),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-cyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dimethyl    titanium),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-cyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dibenzyl    titanium),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-cyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (II)    1,3-pentadiene),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-cyclopenta[b]pyrrol-4-yl)-κN-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (II)    1,4-diphenyl-1,3-butadiene,-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-cyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (III)    2-(N,N-dimethylamino)benzyl),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dichloro    titanium),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dimethyl    titanium),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dibenzyl    titanium),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2)-κN]titanium (II)    1,3-pentadiene),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (II)    1,4-diphenyl-1,3-butadiene,-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2)-κN]titanium (III)    2-(N,N-dimethylamino)benzyl),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dichloro    titanium),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dimethyl    titanium),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dibenzyl    titanium),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (II)    1,3-pentadiene),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (II)    1,4-diphenyl-1,3-butadiene,-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (II)    2-(N,N-diethylamino)benzyl),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-2,5-dimethyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dichloro    titanium),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-2,5-dimethyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dimethyl    titanium),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-2,5-dimethyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dibenzyl    titanium),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-2,5-dimethyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (II)    1,3-pentadiene),-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-2,5-dimethyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (II)    1,4-diphenyl-1,3-butadiene,-   [1-[(3a,4,5,6,6a-η)-1,4-dihydro-2,5-dimethyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (II)    2-(N,N-dimethylamino)benzyl),    and mixtures thereof, especially mixtures of positional isomers.

The skilled artisan will recognize that additional members of theforegoing list, obtainable by substitution of known ligands or differentGroup 3-10 metals for those specifically named, are also included withinthe invention. Moreover, it should also be recognized that all possibleelectronic distributions within the molecule, such as η³, η⁴ or η⁵ areintended to be included by the foregoing named compounds.

The complexes are rendered catalytically active by combination with anactivating cocatalyst or use of an activating technique, such as thosethat are previously known in the art for use with Group 4 metal olefinpolymerization complexes. Suitable activating cocatalysts for use hereininclude polymeric or oligomeric alumoxanes, especially methylalumoxane,triisobutyl aluminum modified methylalumoxane, or isobutylalumoxane;neutral Lewis acids, such as C₁₋₃₀ hydrocarbyl substituted Group 13compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boroncompounds and halogenated (including perhalogenated) derivativesthereof, having from 1 to 10 carbons in each hydrocarbyl or halogenatedhydrocarbyl group, more especially perfluorinated tri(aryl)boroncompounds, and most especially tris(pentafluorophenyl)borane;nonpolymeric, compatible, noncoordinating, ion forming compounds(including the use of such compounds under oxidizing conditions),especially the use of ammonium-, phosphonium-, oxonium-, carbonium-,silylium- or sulfonium-salts of compatible, noncoordinating anions, orferrocenium salts of compatible, noncoordinating anions; bulkelectrolysis (explained in more detail hereinafter); and combinations ofthe foregoing activating cocatalysts and techniques. A preferred ionforming compound is a tri(C₁₋₂₀-hydrocarbyl)ammonium salt of atetrakis(fluoroaryl)borate, especially atetrakis(pentafluorophenyl)borate. The foregoing activating cocatalystsand activating techniques have been previously taught with respect todifferent metal complexes in the following references: EP-A-277,003,U.S. Pat. No. 5,153,157, U.S. Pat. No. 5,064,802, U.S. Pat. No.5,321,106, U.S. Pat. No. 5,721,185, U.S. Pat. No. 5,350,723, U.S. Pat.No. 5,425,872, U.S. Pat. No. 5,625,087, U.S. Pat. No. 5,883,204, U.S.Pat. No. 5,919,983, U.S. Pat. No. 5,783,512, WO 99/15534, and U.S. Ser.No. 09/251,664, filed Feb. 17, 1999 (WO99/42467).

Combinations of neutral Lewis acids, especially the combination of atrialkylaluminum compound having from 1 to 4 carbons in each alkyl groupand a halogenated tri(hydrocarbyl)boron compound having from 1 to 20carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)borane, further combinations of such neutralLewis acid mixtures with a polymeric or oligomeric alumoxane, andcombinations of a single neutral Lewis acid, especiallytris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxaneare especially desirable activating cocatalysts. Preferred molar ratiosof Group 4 metal complex:tris(pentafluoro-phenylborane:alumoxane arefrom 1:1:1 to 1:10:30, more preferably from 1:1:1.5 to 1:5:10.

Suitable ion forming compounds useful as cocatalysts in one embodimentof the present invention comprise a cation which is a Bronsted acidcapable of donating a proton, and a compatible, noncoordinating anion,A⁻. As used herein, the term “noncoordinating” means an anion orsubstance which either does not coordinate to the Group 4 metalcontaining precursor complex and the catalytic derivative derivedtherefrom, or which is only weakly coordinated to such complexes therebyremaining sufficiently labile to be displaced by a neutral Lewis base. Anoncoordinating anion specifically refers to an anion which whenfunctioning as a charge balancing anion in a cationic metal complex doesnot transfer an anionic substituent or fragment thereof to said cationthereby forming neutral complexes. “Compatible anions” are anions whichare not degraded to neutrality when the initially formed complexdecomposes and are noninterfering with desired subsequent polymerizationor other uses of the complex.

Preferred anions are those containing a single coordination complexcomprising a charge-bearing metal or metalloid core which anion iscapable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, said anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitrites. Suitable metals include,but are not limited to, aluminum, gallium, niobium or tantalum. Suitablemetalloids include, but are not limited to, boron, phosphorus, andsilicon. Compounds containing anions which comprise coordinationcomplexes containing a single metal or metalloid atom are, of course,well known and many, particularly such compounds containing a singleboron atom in the anion portion, are available commercially.

Preferably such cocatalysts may be represented by the following generalformula:(L*-H)_(d) ⁺(A)^(d−)

-   -   wherein:

L* is a neutral Lewis base;

-   -   (L*-H)⁺ is a conjugate Bronsted acid of L*;    -   A^(d−) is a noncoordinating, compatible anion having a charge of        d−, and    -   d is an integer from 1 to 3.

More preferably A^(d−) corresponds to the formula: [M′Q₄]⁻;

wherein:

-   -   M′ is boron or aluminum in the +3 formal oxidation state; and    -   Q independently each occurrence is selected from hydride,        dialkylamido, halide, hydrocarbyl, hydrocarbyloxide,        halo-substituted hydrocarbyl, halo-substituted hydrocarbyloxy,        and halo-substituted silylhydrocarbyl radicals (including        perhalogenated hydrocarbyl-perhalogenated hydrocarbyloxy- and        perhalogenated silylhydrocarbyl radicals), said Q having up to        20 carbons with the proviso that in not more than one occurrence        is Q halide. Examples of suitable hydrocarbyloxide Q groups are        disclosed in U.S. Pat. No. 5,296,433.

In a more preferred embodiment, d is one, that is, the counter ion has asingle negative charge and is A⁻. Activating cocatalysts comprisingboron which are particularly useful in the preparation of catalysts ofthis invention may be represented by the following general formula:(L*-H)⁺(BQ₄)⁻;

-   -   wherein:

L* is as previously defined;

-   -   B is boron in a formal oxidation state of 3; and

Q is a hydrocarbyl-, hydrocarbyloxy-, fluorohydrocarbyl-,fluorohydrocarbyloxy-, hydroxyfluorohydrocarbyl-,dihydrocarbylaluminumoxyfluorohydrocarbyl-, or fluorinatedsilylhydrocarbyl-group of up to 20 nonhydrogen atoms, with the provisothat in not more than one occasion is Q hydrocarbyl. Most preferably, Qis each occurrence a fluorinated aryl group, especially, apentafluorophenyl group.

Preferred Lewis base salts are ammonium salts, more preferablytrialkyl-ammonium- or dialkylarylammonium-salts containing one or moreC₁₂₋₄₀ alkyl groups. The latter cocatalysts have been found to beparticularly suitable for use in combination with not only the presentmetal complexes but other Group 4 metallocenes as well.

Illustrative, but not limiting, examples of boron compounds which may beused as an activating cocatalyst in the preparation of the improvedcatalysts of this invention (as well as previously known Group 4 metalcatalysts) are

tri-substituted ammonium salts such as:

-   trimethylammonium tetrakis(pentafluorophenyl)borate,-   triethylammonium tetrakis(pentafluorophenyl)borate,-   tripropylammonium tetrakis(pentafluorophenyl)borate,-   tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,-   tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,-   N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate,-   N,N-dimethylanilinium benzyltris(pentafluorophenyl)borate,-   N,N-dimethylanilinium    tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate,-   N,N-dimethylanilinium    tetrakis(4-(triisopropylsilyl)-2,3,5,6-tetrafluorophenyl)borate,-   N,N-dimethylanilinium    pentafluorophenoxytris(pentafluorophenyl)borate,-   N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-dimethyl-2,4,6-trimethylanilinium    tetrakis(pentafluorophenyl)borate,-   dimethyltetradecylammonium tetrakis(pentafluorophenyl)borate,-   dimethylhexadecylammonium tetrakis(pentafluorophenyl)borate,-   dimethyloctadecylammonium tetrakis(pentafluorophenyl)borate,-   methylditetradecylammonium tetrakis(pentafluorophenyl)borate,-   methylditetradecylammonium    (hydroxyphenyl)tris(pentafluorophenyl)borate,-   methylditetradecylammonium    (diethylaluminoxyphenyl)tris(pentafluorophenyl)borate,-   methyldihexadecylammonium tetrakis(pentafluorophenyl)borate,-   methyldihexadecylammonium    (hydroxyphenyl)tris(pentafluorophenyl)borate,-   methyldihexadecylammonium    (diethylaluminoxyphenyl)tris(pentafluorophenyl)borate,-   methyldioctadecylammonium tetrakis(pentafluorophenyl)borate,-   methyldioctadecylammonium    (hydroxyphenyl)tris(pentafluorophenyl)borate,-   methyldioctadecylammonium    (diethylaluminoxyphenyl)tris(pentafluorophenyl)borate,-   methyldioctadecylammonium tetrakis(pentafluorophenyl)borate,-   phenyldioctadecylammonium tetrakis(pentafluorophenyl)borate,-   phenyldioctadecylammonium    (hydroxyphenyl)tris(pentafluorophenyl)borate,-   phenyldioctadecylammonium    (diethylaluminoxyphenyl)tris(pentafluorophenyl)borate,-   (2,4,6-trimethylphenyl)dioctadecylammonium    tetrakis(pentafluorophenyl)borate,-   (2,4,6-trimethylphenyl)dioctadecylammonium    (hydroxyphenyl)tris(pentafluorophenyl)-borate,-   (2,4,6-trimethylphenyl)dioctadecylammonium (diethylaluminoxyphenyl)    tris(pentafluorophenyl)borate,-   (2,4,6-trifluorophenyl)dioctadecylammonium    tetrakis(pentafluorophenyl)borate,-   (2,4,6-trifluorophenyl)dioctadecylammonium    (hydroxyphenyl)tris(pentafluorophenyl)-borate,-   (2,4,6-trifluorophenyl)dioctadecylammonium    (diethylaluminoxyphenyl)tris(pentafluoro-phenyl) borate,-   (pentafluorophenyl)dioctadecylammonium    tetrakis(pentafluorophenyl)borate,-   (pentafluorophenyl)dioctadecylammonium    (hydroxyphenyl)tris(pentafluorophenyl)-borate,-   (pentafluorophenyl)dioctadecylammonium    (diethylaluminoxyphenyl)tris(pentafluoro-phenyl) borate,-   (p-trifluoromethylphenyl)dioctadecylammonium    tetrakis(pentafluorophenyl)borate,-   (p-trifluoromethylphenyl)dioctadecylammonium    (hydroxyphenyl)tris(pentafluoro-phenyl) borate,-   (p-trifluoromethylphenyl)dioctadecylammonium    (diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,-   p-nitrophenyldioctadecylammonium tetrakis(pentafluorophenyl)borate,-   p-nitrophenyldioctadecylammonium    (hydroxyphenyl)tris(pentafluorophenyl)borate,-   p-nitrophenyldioctadecylammonium    (diethylaluminoxyphenyl)tris(pentafluorophenyl)borate, and mixtures    of the foregoing,    -   dialkyl ammonium salts such as:    -   di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,-   methyloctadecylammonium tetrakis(pentafluorophenyl)borate,-   methyloctadodecylammonium tetrakis(pentafluorophenyl)borate, and-   dioctadecylammonium tetrakis(pentafluorophenyl)borate;    -   tri-substituted phosphonium salts such as:    -   triphenylphosphonium tetrakis(pentafluorophenyl)borate,-   methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate, and-   tri(2,6-dimethylphenyl)phosphonium    tetrakis(pentafluorophenyl)borate;    -   di-substituted oxonium salts such as:    -   diphenyloxonium tetrakis(pentafluorophenyl)borate,-   di(o-tolyl)oxonium tetrakis(pentafluorophenyl)borate, and-   di(octadecyl)oxonium tetrakis(pentafluorophenyl)borate;    -   di-substituted sulfonium salts such as:-   di(o-tolyl)sulfonium tetrakis(pentafluorophenyl)borate, and-   methylcotadecylsulfonium tetrakis(pentafluorophenyl)borate.

Preferred trialkylammonium cations are methyldioctadecylammonium anddimethyloctadecylammonium. The use of the above Bronsted acid salts asactivating cocatalysts for addition polymerization catalysts is known inthe art, having been disclosed in U.S. Pat. Nos. 5,064,802, 5,919,983,5,783,512 and elsewhere. Preferred dialkylarylammonium cations arefluorophenyldioctadecylammonium-, perfluoro-phenyldioctacecylammonium-and p-trifluoromethylphenyldi(octadecyl)ammonium cations. It should benoted that certain of the cocatalysts, especially those containing ahydroxyphenyl ligand in the borate anion, may require the addition of aLewis acid, especially a trialkylaluminum compound, to thepolymerization mixture or the catalyst composition, in order to form theactive catalyst composition.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:(Ox^(e+))_(d)(A^(d−))_(e).

-   -   wherein:    -   Ox^(e+) is a cationic oxidizing agent having a charge of e+;    -   e is an integer from 1 to 3; and

A^(d−) and d are as previously defined.

Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺ or Pb⁺². Preferred embodimentsof A^(d−) are those anions previously defined with respect to theBronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate. The use of the above salts asactivating cocatalysts for addition polymerization catalysts is known inthe art, having been disclosed in U.S. Pat. No. 5,321,106.

Another suitable ion forming, activating cocatalyst comprises a compoundwhich is a salt of a carbenium ion and a noncoordinating, compatibleanion represented by the formula:{circle over (C)}⁺A⁻

-   -   wherein:    -   {circle over (C)}⁺ is a C₁₋₂₀ carbenium ion; and    -   A⁻ is as previously defined. A preferred carbenium ion is the        trityl cation, that is triphenylmethylium. The use of the above        carbenium salts as activating cocatalysts for addition        polymerization catalysts is known in the art, having been        disclosed in U.S. Pat. No. 5,350,723.

A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silylium ion and a noncoordinating,compatible anion represented by the formula:R³ ₃Si(X′)_(q) ⁺A⁻

-   -   wherein:    -   R³ is C₁₋₁₀ hydrocarbyl, and X′, q and A⁻ are as previously        defined.

Preferred silylium salt activating cocatalysts are trimethylsilyliumtetrakispentafluorophenylborate, triethylsilyliumtetrakispentafluorophenylborate and ether substituted adducts thereof.The use of the above silylium salts as activating cocatalysts foraddition polymerization catalysts is known in the art, having beendisclosed in U.S. Pat. No. 5,625,087.

Certain complexes of alcohols, mercaptans, silanols, and oximes withtris(pentafluorophenyl)borane are also effective catalyst activators andmay be used according to the present invention. Such cocatalysts aredisclosed in U.S. Pat. No. 5,296,433.

Another class of suitable catalyst activators are expanded anioniccompounds corresponding to the formula: (A^(1+a) ¹ )_(b) ₁ (Z¹J¹ _(j) ₁)^(−c1) _(d) ₁ ,

-   -   wherein:

A¹ is a cation of charge +a¹,

-   -   Z¹ is an anion group of from 1 to 50, preferably 1 to 30 atoms,        not counting hydrogen atoms, further containing two or more        Lewis base sites;    -   J¹ independently each occurrence is a Lewis acid coordinated to        at least one Lewis base site of Z¹, and optionally two or more        such J¹ groups may be joined together in a moiety having        multiple Lewis acidic functionality,    -   j¹ is a number from 2 to 12 and    -   a¹, b¹, c¹, and d¹ are integers from 1 to 3, with the proviso        that a¹×b¹ is equal to c¹×d¹.

The foregoing cocatalysts (illustrated by those having imidazolide,substituted imidazolide, imidazolinide, substituted imidazolinide,benzimidazolide, or substituted benzimidazolide anions) may be depictedschematically as follows:

-   -   wherein:    -   A¹⁺ is a monovalent cation as previously defined, and preferably        is a trihydrocarbyl ammonium cation, containing one or two        C₁₀₋₄₀ alkyl groups, especially the        methylbis(tetradecyl)ammonium- or        methylbis(octadecyl)ammonium-cation,    -   R⁸, independently each occurrence, is hydrogen or a halo,        hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or        silyl, (including mono-, di- and tri(hydrocarbyl)silyl) group of        up to 30 atoms not counting hydrogen, preferably C₁₋₂₀ alkyl,        and    -   J¹ is tris(pentafluorophenyl)borane or        tris(pentafluorophenyl)aluminane.

Examples of these catalyst activators include thetrihydrocarbylammonium-, especially, methylbis(tetradecyl)ammonium- ormethylbis(octadecyl)ammonium-salts of:

-   bis(tris(pentafluorophenyl)borane)imidazolide,-   bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide,    bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolide,    bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolide,-   bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide,-   bis(tris(pentafluorophenyl)borane)imidazolinide,-   bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide,-   bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolinide,-   bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolinide,-   bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolinide,-   bis(tris(pentafluorophenyl)borane)-5,6-dimethylbenzimidazolide,-   bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide,-   bis(tris(pentafluorophenyl)alumane)imidazolide,-   bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide,-   bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide,-   bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolide,-   bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolide,-   bis(tris(pentafluorophenyl)alumane)imidazolinide,-   bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide,-   bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolinide,-   bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolinide,-   bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolinide,-   bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide, and-   bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.

A further class of suitable activating cocatalysts include cationicGroup 13 salts corresponding to the formula:[M″Q¹ ₂L′_(1′)]⁺(Ar^(f) ₃M′Q²)⁻

-   -   wherein:    -   M″ is aluminum, gallium, or indium;    -   M′ is boron or aluminum;    -   Q⁻¹ is C₁₋₂₀ hydrocarbyl, optionally substituted with one or        more groups which independently each occurrence are        hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino,        di(hydrocarbylsilyl)amino, hydrocarbylamino,        di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, or        hydrocarbylsulfido groups having from 1 to 20 atoms other than        hydrogen, or, optionally, two or more Q¹ groups may be        covalently linked with each other to form one or more fused        rings or ring systems;    -   Q² is an alkyl group, optionally substituted with one or more        cycloalkyl or aryl groups, said Q² having from 1 to 30 carbons;

-   L′ is a monodentate or polydentate Lewis base, preferably L′ is    reversibly coordinated to the metal complex such that it may be    displaced by an olefin monomer, more preferably L′ is a monodentate    Lewis base;    -   1′ is a number greater than zero indicating the number of Lewis        base moieties, L′, and    -   Ar^(f) independently each occurrence is an anionic ligand group;        preferably Ar^(f) is selected from the group consisting of        halide, C₁₋₂₀ halohydrocarbyl, and Q¹ ligand groups, more        preferably Ar^(f) is a fluorinated hydrocarbyl moiety of from 1        to 30 carbon atoms, most preferably Ar^(f) is a fluorinated        aromatic hydrocarbyl moiety of from 6 to 30 carbon atoms, and        most highly preferably Ar^(f) is a perfluorinated aromatic        hydrocarbyl moiety of from 6 to 30 carbon atoms.

Examples of the foregoing Group 13 metal salts are alumiciniumtris(fluoroaryl)borates or gallicinium tris(fluoroaryl)boratescorresponding to the formula: [M″Q¹ ₂L′_(1′)]⁺(Ar^(f) ₃BQ²)⁻, wherein M″is aluminum or gallium; Q¹ is C₁₋₂₀ hydrocarbyl, preferably C₁₋₈ alkyl;Ar^(f) is perfluoroaryl, preferably pentafluorophenyl; and Q² is C₁₋₈alkyl, preferably C₁₋₈ alkyl. More preferably, Q¹ and Q² are identicalC₁₋₈ alkyl groups, most preferably, methyl, ethyl or octyl.

The foregoing activating cocatalysts may also be used in combination. Anespecially preferred combination is a mixture of atri(hydrocarbyl)aluminum or tri(hydrocarbyl)borane compound having from1 to 4 carbons in each hydrocarbyl group or an ammonium borate with anoligomeric or polymeric alumoxane compound.

The molar ratio of catalyst/cocatalyst employed preferably ranges from1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferablyfrom 1:1000 to 1:1. Alumoxane, when used by itself as an activatingcocatalyst, is employed in large quantity, generally at least 100 timesthe quantity of metal complex on a molar basis.Tris(pentafluorophenyl)borane, where used as an activating cocatalyst isemployed in a molar ratio to the metal complex of form 0.5:1 to 10:1,more preferably from 1:1 to 6:1 most preferably from 1:1 to 5:1. Theremaining activating cocatalysts are generally employed in approximatelyequimolar quantity with the metal complex.

The catalysts, whether or not supported in any suitable manner, may beused to polymerize ethylenically unsaturated monomers having from 2 to100,000 carbon atoms either alone or in combination. Preferred additionpolymerizable monomers for use herein include olefins, diolefins andmixtures thereof. Preferred olefins are aliphatic or aromatic compoundscontaining vinylic unsaturation as well as cyclic compounds containingethylenic unsaturation. Examples of the latter include cyclobutene,cyclopentene, norbornene, and norbornene derivatives that aresubstituted in the 5- and 6-positions with C₁₋₂₀ hydrocarbyl groups.Preferred diolefins are C₄₋₄₀ diolefin compounds, including ethylidenenorbornene, 1,4-hexadiene, and norbornadiene. The catalysts andprocesses herein are especially suited for use in preparation ofethylene/1-butene, ethylene/1-hexene, ethylene/styrene,ethylene/propylene, ethylene/1-pentene, ethylene/4-methyl-1-pentene andethylene/1-octene copolymers as well as terpolymers of ethylene,propylene and a nonconjugated diene, such as, for example, EPDMterpolymers.

Most preferred monomers include the C₂₋₂₀ α-olefins, especiallyethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, long chainmacromolecular α-olefins, and mixtures thereof. Other preferred monomersinclude styrene, C₁₋₄ alkyl substituted styrene, ethylidenenorbornene,1,4-hexadiene, 1,7-octadiene, vinylcyclohexane, 4-vinylcyclohexene,divinylbenzene, and mixtures thereof with ethylene. Long chainmacromolecular α-olefins are vinyl terminated polymeric remnants formedin situ during continuous solution polymerization reactions. Undersuitable processing conditions such long chain macromolecular units arereadily polymerized into the polymer product along with ethylene andother short chain olefin monomers to give small quantities of long chainbranching in the resulting polymer.

Preferred monomers include a combination of ethylene and one or morecomonomers selected from monovinyl aromatic monomers,4-vinylcyclohexene, vinylcyclohexane, norbornadiene,ethylidene-norbornene, C₃₋₁₀ aliphatic α-olefins (especially propylene,isobutylene, 1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene,and 1-octene), and C₄₋₄₀ dienes. Most preferred monomers are mixtures ofethylene and styrene; mixtures of ethylene, propylene and styrene;mixtures of ethylene, styrene and a nonconjugated diene, especiallyethylidenenorbornene or 1,4-hexadiene, and mixtures of ethylene,propylene and a nonconjugated diene, especially ethylidenenorbornene or1,4-hexadiene.

In general, the polymerization may be accomplished at conditions wellknown in the prior art for Ziegler-Natta or Kaminsky-Sinn typepolymerization reactions, that is, temperatures from 0-250° C.,preferably 30 to 200° C. and pressures from atmospheric to 10,000atmospheres. Suspension, solution, slurry, gas phase, solid state powderpolymerization or other process condition may be employed if desired. Asupport, especially silica, alumina, or a polymer (especiallypoly(tetrafluoroethylene) or a polyolefin) may be employed, anddesirably is employed when the catalysts are used in a gas phasepolymerization process. The support is preferably employed in an amountto provide a weight ratio of catalyst (based on metal):support from1:10⁶ to 1:10³, more preferably from 1:10⁶ to 1:10⁴.

In most polymerization reactions the molar ratio ofcatalyst:polymerizable compounds employed is from 10⁻¹²:1 to 10⁻¹:1,more preferably from 10⁻⁹:1 to 10⁻⁵:1.

Suitable solvents use for solution polymerization are liquids that aresubstantially inert under process conditions encountered in their usage.Examples include straight and branched-chain hydrocarbons such asisobutane, butane, pentane, hexane, heptane, octane, and mixturesthereof; cyclic and alicyclic hydrocarbons such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof; perfluorinated hydrocarbons such as perfluorinated C₄₋₁₀alkanes, and alkyl-substituted aromatic compounds such as benzene,toluene, xylene, and ethylbenzene. Suitable solvents also include liquidolefins which may act as monomers or comonomers.

The catalysts may be utilized in combination with at least oneadditional homogeneous or heterogeneous polymerization catalyst in thesame reactor or in separate reactors connected in series or in parallelto prepare polymer blends having desirable properties. An example ofsuch a process is disclosed in WO 94/00500.

The catalysts of the present invention are particularly advantageous forthe production of ethylene homopolymers and ethylene/α-olefin copolymershaving high levels of long chain branching. The use of the catalysts ofthe present invention in continuous polymerization processes, especiallycontinuous, solution polymerization processes, allows for elevatedreactor temperatures which favor the formation of vinyl terminatedpolymer chains that may be incorporated into a growing polymer, therebygiving a long chain branch. The use of the present catalyst compositionsadvantageously allows for the economical production of ethylene/α-olefincopolymers having processability similar to high pressure, free radicalproduced low density polyethylene.

The present catalyst compositions may be advantageously employed toprepare olefin polymers having improved processing properties bypolymerizing ethylene alone or ethylene/α-olefin mixtures with lowlevels of a “H” branch inducing diene, such as norbornadiene,1,7-octadiene, or 1,9-decadiene. The unique combination of elevatedreactor temperatures, high molecular weight (or low melt indices) athigh reactor temperatures and high comonomer reactivity advantageouslyallows for the economical production of polymers having excellentphysical properties and processability. Preferably such polymerscomprise ethylene, a C₃₋₂₀ α-olefin and a “H”-branching comonomer.Preferably, such polymers are produced in a solution process, mostpreferably a continuous solution process.

The catalyst composition may be prepared as a homogeneous catalyst byaddition of the requisite components to a solvent or diluent in whichpolymerization will be conducted. The catalyst composition may also beprepared and employed as a heterogeneous catalyst by adsorbing,depositing or chemically attaching the requisite components on aninorganic or organic particulated solid. Examples of such solidsinclude, silica, silica gel, alumina, clays, expanded clays (aerogels),aluminosilicates, trialkylaluminum compounds, and organic or inorganicpolymeric materials, especially polyolefins. In a preferred embodiment,a heterogeneous catalyst is prepared by reacting an inorganic compound,preferably a tri(C₁₋₄ alkyl)aluminum compound, with an activatingcocatalyst, especially an ammonium salt of ahydroxyaryl(trispentafluorophenyl)borate, such as an ammonium salt of(4-hydroxy-3,5-ditertiarybutylphenyl)tris(pentafluorophenyl)borate or(4-hydroxyphenyl) tris(pentafluorophenyl)borate. This activatingcocatalyst is deposited onto the support by coprecipitating, imbibing,spraying, or similar technique, and thereafter removing any solvent ordiluent. The metal complex is added to the support, also by adsorbing,depositing or chemically attaching the same to the support, eithersubsequently, simultaneously or prior to addition of the activatingcocatalyst.

When prepared in heterogeneous or supported form, the catalystcomposition is employed in a slurry or gas phase polymerization. As apractical limitation, slurry polymerization takes place in liquiddiluents in which the polymer product is substantially insoluble.Preferably, the diluent for slurry polymerization is one or morehydrocarbons with less than 5 carbon atoms. If desired, saturatedhydrocarbons such as ethane, propane or butane may be used in whole orpart as the diluent. Likewise, the α-olefin monomer or a mixture ofdifferent α-olefin monomers may be used in whole or part as the diluentMost preferably, at least a major part of the diluent comprises theα-olefin monomer or monomers to be polymerized. A dispersant,particularly an elastomer, may be dissolved in the diluent utilizingtechniques known in the art, if desired.

At all times, the individual ingredients as well as the recoveredcatalyst components must be protected from oxygen and moisture.Therefore, the catalyst components and catalysts must be prepared andrecovered in an oxygen and moisture free atmosphere. Preferably,therefore, the reactions are performed in the presence of an dry, inertgas, such as, for example, nitrogen.

The polymerization may be carried out as a batchwise or a continuouspolymerization process. A continuous process is preferred, in whichevent catalyst, ethylene, comonomer, and optionally solvent, arecontinuously supplied to the reaction zone, and polymer productcontinuously removed therefrom.

Without limiting in any way the scope of the invention, one means forcarrying out such a polymerization process is as follows: In astirred-tank reactor, the monomers to be polymerized are introducedcontinuously, together with solvent and an optional chain transferagent. The reactor contains a liquid phase composed substantially ofmonomers, together with any solvent or additional diluent and dissolvedpolymer. If desired, a small amount of a “H”-branch inducing diene suchas norbornadiene, 1,7-octadiene or 1,9-decadiene may also be added.Catalyst and cocatalyst are continuously introduced in the reactorliquid phase. The reactor temperature and pressure may be controlled byadjusting the solvent/monomer ratio, the catalyst addition rate, as wellas by cooling or heating coils, jackets or both. The polymerization rateis controlled by the rate of catalyst addition. The ethylene content ofthe polymer product is determined by the ratio of ethylene to comonomerin the reactor, which is controlled by manipulating the respective feedrates of these components to the reactor. The polymer product molecularweight is controlled, optionally, by controlling other polymerizationvariables such as the temperature, monomer concentration, or by thepreviously mention chain transfer agent, such as a stream of hydrogenintroduced to the reactor, as is well known in the art. The reactoreffluent is contacted with a catalyst kill agent such as water. Thepolymer solution is optionally heated, and the polymer product isrecovered by flashing off gaseous monomers as well as residual solventor diluent at reduced pressure, and, if necessary, conducting furtherdevolatilization in equipment such as a devolatilizing extruder. In acontinuous process the mean residence time of the catalyst and polymerin the reactor generally is from 5 minutes to 8 hours, and preferablyfrom 10 minutes to 6 hours.

Ethylene homopolymers and ethylene/α-olefin copolymers are particularlysuited for preparation according to the invention. Generally suchpolymers have densities from 0.85 to 0.96 g/ml. Typically the molarratio of α-olefin comonomer to ethylene used in the polymerization maybe varied in order to adjust the density of the resulting polymer. Whenproducing materials with a density range of from 0.91 to 0.93 thecomonomer to monomer ratio is less than 0.2, preferably less than 0.05,even more preferably less than 0.02, and may even be less than 0.01. Inthe above polymerization process hydrogen has been found to effectivelycontrol the molecular weight of the resulting polymer. Typically, themolar ratio of hydrogen to monomer is less than 0.5, preferably lessthan 0.2, more preferably less than 0.05, even more preferably less than0.02 and may even be less than 0.01.

EXAMPLES

It is understood that the present invention is operable in the absenceof any component which has not been specifically disclosed. Thefollowing examples are provided in order to further illustrate theinvention and are not to be construed as limiting. Unless stated to thecontrary, all parts and percentages are expressed on a weight basis. Theterm “overnight”, if used, refers to a time of approximately 16-18hours, “room temperature”, if used, refers to a temperature of about20-25° C., and “mixed alkanes” refers to a mixture of hydrogenatedpropylene oligomers, mostly C₆-C₁₂ isoalkanes, available commerciallyunder the trademark Isopar E™ from Exxon Chemicals Inc. In the event anycompound depicted by a structural formula is incorrectly named, theformula shall be controlling.

All solvents were purified using the technique disclosed by Pangborn etal, Organometallics, 15, 1518-1520, (1996). ¹H and ¹³C NMR shifts werereferenced to internal solvent resonances and are reported relative toTMS.

Example 1[1-[(3a,4,5,6,6a-η)-1,4-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dichlorotitanium

1-Phenylpyrrole-2-carbaldehyde In a nitrogen purged one liter flaskequipped with a mechanical stirrer were placed 16.2 mL ofdimethylformamide followed by slow addition of 19 mL of POCl₃. Themixture was stirred for 10 minutes, then cooled to 0° C. To the mixturewas added a solution of 25 g of 1-phenylpyrrole in 25 mL ofdichloromethane. The mixture was allowed to warm to room temperature (10minutes) and was then heated to 50° C. for one hour. The contents werethen cooled to room temperature and the flask was opened to the air and220 g of crushed ice were added, followed by 250 mL of 20 percentaqueous NaOH. The mixture was immediately warmed to 85° C. and stirredfor 10 minutes, then the flask was cooled to room temperature using anice bath. The reaction mixture was extracted with dichloromethane (3×100mL) and the combined organic fractions were washed with water (2×200mL). The organic fraction was then dried with sodium sulfate and thevolatiles removed in a rotary evaporator to leave an orange oil (24.4 g,82 percent). The product contained 10 percent of the1-phenylpyrrole-3-carbaldehyde isomer, and was used without furtherpurification.

¹H NMR (CDCl₃): 6.35 (dd, 1H), 7.0 (t, 1H), 7.1 (dd, 1H), 7.3 (m, 2H),7.4 (m, 3H), 9.5 (s, 1H); ¹³C {¹H} NMR (CDCl₃) 178.4, 138.2, 132.0,130.6, 128.6, 127.7, 125.5, 121.5, 110.4.

Ethyl-(2Z)-2-methyl-3-[1-phenylpyrrol-2-yl]prop-2-enoate Into a 250 mLflask, a solution of triethyl 2-phosphonopropionate (32 mL, 150 mmoles)in 20 mL of THF was added slowly to a mixture of sodium hydride (4.8 g,200 mmoles) in 10 mL of THF at 0° C. The slurry was warmed to roomtemperature and stirred for one hour; the temperature was lowered to−10° C. Then a solution of 1-phenylpyrrole-2-carbaldehyde (24.4 g, 142mmoles) in 50 mL of THF was added in a period of 10 minutes. The mixtureslowly formed a precipitate. The precipitate was partially broken with aspatula and the reaction mixture was slowly warmed to room temperatureover 30 minutes. A saturated aqueous solution of NH₄Cl (20 mL) wascarefully added. The product was extracted in ether (2×100 mL), theether extracts washed with brine and dried over sodium sulfate. Thesolvent was removed in a rotary evaporator, and the crude product waswashed with hexane to give an orange oil. The oil crystallized over aperiod of several days and was triturated with small portions of hexane(5×10 mL), filtered and the solid dried in vacuo to give 25.8 g (71percent) of a light-tan crystalline material.

¹H NMR (CDCl₃): 7.4 (m, 4H), 7.3 (m, 2H), 7.0 (dd, 1H), 6.7 (dd, 1H),6.4 (t, 1H), 4.1 (q, 2H), 2.2 (d, 3H), 1.2 (t, 3); ¹³C {¹H} NMR (CDCl₃)168.8, 139.2, 129.6, 129.2, 127.6, 127.5, 126.3, 125.0, 122.9, 114.3,110.2, 60.4, 14.3, 14.2.

Ethyl [2-Methyl-3-(1-phenylpyrrol-2-yl)]propanoate In a 300 mL Parrreactor were charged 12.0 g (47 mmoles) ofethyl-(2Z)-2-methyl-3-[1-phenylpyrrol-2-yl]prop-2-enoate, 0.6 g of 10percent Pd on carbon and 150 mL of methylene chloride. The reactor waspressurized to 80 psig (660 kPa) with hydrogen; after one hour thepressure had dropped to 40 psig (380 kPa), the reactor was repressurizedto 100 psig (790 kPa) with hydrogen and the mixture was stirredovernight. The next day the residual pressure of hydrogen was vented andthe reactor was purged with nitrogen. The catalyst was filtered off andthe filtrate was dried in a rotary evaporator to leave the product as aliquid: 12.5 g (103 percent).

¹H NMR (CDCl₃): 7.3-7.4 (m, 5H), 6.7 (m, 1H), 6.2 (m, 1H), 6.0 (m, 1H),4.0 (q, 2H), 2.9 (m, 1H), 2.5 (m, 2H), 1.2 (t, 3H), 1.0 (d, 3H); ¹³C{¹H} NMR (CDCl₃) 175.8, 140.1, 130.7, 129.0, 127.1, 126.2, 121.8, 111.7,107.9, 60.1, 39.4, 30.4, 17.0, 14.0.

2-Methyl-3-[1-phenylpyrrol-2-yl]propanoic acid In a 500 mL flask wereplaced 12.5 g (48.6 mmoles) of ethyl[2-methyl-3-(1-phenylpyrrol-2-yl)]propanoate, and then 250 mL ofClaisen's alkali (350 g KOH+250 mL water; cool and dilute to one literwith methanol) was added. The mixture was heated to 90° C. for one hour.The yellowish solution was poured over crushed ice and then enough 6MHCl was added to acidify the solution to pH 1-2. The precipitated freeacid was extracted with ether (3×300 mL), the ether washes with brine,and dried with anhydrous sodium sulfate. The volatiles were removed in arotary evaporator. The product was recovered as a yellow liquid: 9.5 g(85 percent).

¹H NMR (CDCl₃): 9.6 (br, 1H), 7.3-7.4 (m, 5H), 6.7 (m, 1H), 6.2 (m, 1H),6.1 (m, 1H), 3.5 (q, 2H), 3.0 (m, 1H), 2.6 (m, 2H), 1.2 (t, 3H), 1.1 (d,3H); ¹³C {¹H} NMR (CDCl₃) 182.2, 140.0, 130.5, 129.1, 127.3, 126.3,122.2, 108.1, 108.0, 65.8, 39.5, 30.0, 16.8, 15.1.

5,6-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4(1H)-one Superpolyphosphoric acid (SPPA) was prepared by mixing 41 g of P₂O₅ in 250 gof polyphosphoric acid at 140° C. until all of the P₂O₅ dissolved. TheSPPA was cooled to 100° C. and then a solution made with 9.5 g (41.4mmoles) of 2-methyl-3-[1-phenylpyrrol-2-yl]propanoic acid, in 20 mL of1,2-dichloroethane was added dropwise. The mixture was stirred for fivehours, cooled to 60° C. and poured slowly onto water. After completebreakdown of the clumpy reaction mixture, the product was extracted withdichloromethane, the organic phase was washed with NaHCO₃, and driedwith Na₂SO₄. The volatiles were removed on a rotary evaporator, leavinga tan solid. Yield: 8.5 g (97 percent)

¹H NMR (CDCl₃): 1.34 (d, 3H), 2.65 (dd, 1H), 3.0 (pd, 1H), 3.3 (dd, 1H),6.5 (d, 1H), 7.1 (d, 1H), 7.4 (m, 3H), 7.5 (m, 2H); ¹³C {¹H} NMR(CDCl₃): 17.0, 30.7, 47.4, 104.0, 121.9, 127.0, 127.8, 129.7, 138.6,156.4, 199.5.

5,6-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4(1H)-one tosylhydrazone A mixture containing5,6-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4(1H)-one (8.5 g, 40.2mmol), p-toluene sulfonyl hydrazide (7.7 g, 41 mmoles) and p-toluenesulfonic acid monohydrate (1 g, 5 mmoles) were stirred overnight in 60mL of ethanol at 70° C. The solution was cooled in the freezer for a fewhours and the precipitated product was collected, washed with ether anddried in vacuum to give a tan solid (7.7 g, 50 percent), m.p. 175-6° C.

¹H NMR (CDCl₃): 7.9 (d, 2H), 7.45 (m, 2H), 7.3 (m, 6H), 7.05 (d, 1H),6.56 (d, 1H), 3.4 (pd, 1H), 3.2 (dd, 1H), 2.55 (dd, 1H), 2.4 (s, 3H),1.25 (d, 3H); ¹³C {¹H} NMR (CDCl₃): 19.6, 21.5, 32.3, 42.7, 105.5,121.3, 121.7, 126.3, 126.9, 128.1, 129.2, 129.7, 135.4, 138.8, 143.5,147.1, 162.3.

1,6-Dihydro-5-methyl-1-phenylcyclopenta[b]pyrrole To a mixture of5,6-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4(1H)-one tosylhydrazone (7.55 g, 19.9 mmol) in 80 mL of THF was added 26 mL of n-BuLi(1.6 M, hexanes; 2.1 equiv., 41.8 mmoles) at −78° C. in about fiveminutes. The dark brown mixture was slowly allowed to warm up to roomtemperature, and was stirred overnight. A saturated solution of NH₄Cl(10 mL) was carefully added, and the volatiles were removed in a rotaryevaporator. Water (100 mL) was added to the solid residue and themixture was extracted with ether (2×100 mL). The ether layers werecombined and dried with Na₂SO₄, then the volatiles were removed in arotary evaporator to leave 4.7 g of a brownish-yellow oil, to which wasadded 80 mL of hexane and the mixture stirred for 30 minutes; repeatedthe process once more. The filtered extracts were combined and dried invacuo to give 2.4 g (62 percent) of an orange-yellow oil. NMR analysisshowed the presence of two isomers.

¹H NMR (CDCl₃): 7.5 (m, 4H), 7.3 (m, 1H), 7.1 (d, 1H), 6.95* (d, 1H),6.55* (br s, 1H), 6.4 (br s, 1H), 6.35* (d, 1H), 6.25 (d, 1), 3.3 (br s,H), 3.1* (br s, 1H), 2.21* (s, 3H), 2.15 (s, 3H); peaks marked with *are from the least abundant (40 percent)isomer in the final product.

1-(1,4-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-1,1-dimethylethyl)-1,1-dimethylsilanamineTo a mixture of 1,6-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrole (2.41g, 12.3 mmol) in 50 mL of hexanes were added 7.9 mL of butyl lithium(1.6 M hexane; 1.02 equiv.). The mixture was stirred overnight,filtered, the solid was washed with hexanes and dried 2.3 g (92percent), then redissolved in 60 mL of THF. Then a solution ofMe₂SiCl(NH^(t)Bu) (1.94 g, 1.03 equiv.; 11.7 mmoles) in 20 mL of THF wasadded and the solution was stirred overnight. The volatiles were pumpedoff, the residue extracted with hexane, filtered and the filtrate wasthen dried in vacuo to give 3.75 g (94 percent) of a dark orange oil.

¹H NMR (C₆D₆): 7.3 (m, 2H), 7.05 (m, 1H), 6.9 (m, 1H), 6.5 (m, 1H), 6.4(d, 1H), 3.1 (s, 1H), 2.2 (s, 3H), 1.1 (s, 9H),m 0.5 (br s, 1H), 0.2 (s,3H), −0.1 (s, 3H).

[1-[(3a,4,5,6,6a-η)-1,4-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl-1,1-dimethylsilanamato(2-)-κN]dichlorotitanium Into a 100 mL jar were placed 0.50 g (0.41 mmoles) ofN-(1,1-dimethylethyl)-1-(1-phenyl-5-methyl-4H-cyclopenta[b]aza-4-yl)-1,1-dimethylsilanamine,60 mL of hexane, and then 2.0 mL of BuLi (1.6M, hexanes) were added. Themixture was stirred overnight. A small amount of solid precipitated. Thevolatiles were removed in vacuo and the residues redissolved in 20 mL ofTHF. This was followed by addition of 0.57 g (0.41 mmoles) ofTiCl₃.3THF. The mixture was stirred for thirty minutes and then PbCl₂(300 mg, 1.3 electron equivalents) was added, followed by 10 mL ofCH₂Cl₂. After one hour the volatiles were removed in vacuo. The residuewas dissolved in hexane (60 mL) and filtered. The hexane insolublebrick-red material (0.69 g) was extracted with benzene, filtered and thefiltrate dried in vacuo. Yield: 0.37 g (54 percent)

¹H NMR (C₆D₆): 7.2 (d, 2H), 7.03 (t, 2H), 7.0 (d, 1H), 6.9 (t, 1H), 6.43(s, 1H), 6.15 (d, 1H), 2.2 (s, 3H), 1.4 (s, 9H), 0.6 (s, 3H), 0.5 (s,3H); ¹³C {¹H} NMR (C₆D₆) 143.2, 135.2, 129.9, 126.0, 121.0, 107.3,105.7, 61.5, 32.6, 20.0, 3.8, 3.4.

Example 2[1-[(3a,4,5,6,6a-η)-1,4-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dimethyltitanium)

Into a 120 mL jar were placed 0.37 g (0.84 mmoles) of[1-[(3a,4,5,6,6a-η)-1,4-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dichlorotitanium (from example 1), 30 mL of ether and 40 mL of THF. Then 0.6 mLof MeMgI (3M, ether, 1.8 mmoles) were added. The mixture was stirred forone hour, the volatiles removed in vacuo, the residue extracted withhexane, filtered, dried in vacuo (0.33 g), redissolved once more inhexane and filtered, and the filtrate concentrated down to about 5 mL.The solution was placed overnight in the −30° C. freezer. Thesupernatant was separated from the crystals formed. Yield: 0.19 g ofyellow crystals.

¹H NMR (C₆D₆): 0.1 (s, 3H), 0.50 (s, 3H), 0.52 (s, 3H), 1.8 (s, 9H), 2.0(s, 3H), 6.1 (d, 2H), 6.6 (s, 1H), 6.9 (t, 2H), 7.1 (m), 7.2 (d); ¹³C{¹H} NMR (C₆D₆): 4.2, 4.8, 18.6, 34.5, 49.5, 55.7, 57.5, 83.8, 103.7,105.8, 119.4, 124.7, 129.9, 130.4, 131.6, 137.7, 140.5.

Example 3[1-[(3a,4,5,6,6a-η)-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]bis(N,N-dimethylaminotitanium)

3-bromo-2-methyl-thiophene A 500 mL flask was charged with 12 mL (85mmol) of diisopropylamine, 150 mL of ether THF and the system cappedwith an addition funnel/septum and the system purged with nitrogen andcooled to 0° C. To this was added over 20 minutes 3.5 mL of nBuLi (85mmol, 1.6 M in hexanes). After adding all the reagent, the reaction wasstirred for an additional 15 minutes and then the solution cooled to−78° C. To this was added over 30 minutes a 100 mL THF solutioncontaining 8 mL (85 mmol) of 3-bromo-thiophene. After the addition wascomplete, the solution was allowed to warm to 0° C. and stirred for 15minutes. The solution was again cooled to −78° C. and to this added 5.4mL (85 mmol) of iodomethane in 50 mL of THF. The solution was allowed towarm to room temperature and stirred for 1.5 hrs. The solution wascooled to 0° C. and quenched with 100 mL of 1 M HCl(aq). The water layerwas separated and washed with 100 mL of ether and the ether layerseparated. The organic extracts were combined, dried over magnesiumsulfate, filtered and the volatiles removed by rotary evaporation toleave 13.7 g of oil (90 percent).

¹H NMR (CDCl₃): 7.08 (d, 1H), 6.90 (d, 1H), 2.44 (s, 3H). ¹³C{¹H} NMR(CDCl₃): 134.35, 130.15, 122.99, 109.65, 68.22, 31.88, 25.90, 14.83.

2-methyl-3-phenyl-thiophene A 500 mL flask was charged with 13.7 g (77mmol) of 3-bromo-2-methyl-thiophene, 0.21 g (0.40 mmol) of NiCl₂(dppp)and 250 mL of ether. The addition funnel was charged with 26 ml ofphenyl magnesium bromide (77 mmol, 3.0 M in ether) and the Grignardslowly added to the thiophene solution over 1 hour with cooling in anice bath was utilized to cool the reaction during the addition. Afteradding all the Grignard, the reaction was stirred at room temperaturefor 3 hours, cooled to 0° C. and quenched with 100 mL of 1 M HCl(aq).The organic layer was separated and the water solution extracted twicewith 75 mL of diethyl ether. The organic extracts were combined, driedover magnesium sulfate, filtered and the volatiles removed in vacuo toleave 13.3 g (99 percent) of an orange oil.

¹HNMR (CDCl₃): 7.7-7.4 (m, 5H), 7.2 (m, 2H), 2.66 (s, 3H). ¹³C{¹H}NMR(CDCl₃): 139.06, 137.19, 134.50, 129.62, 129.08, 128.80, 127.57,127.07, 121.94, 14.53.

5,6-dihydro-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thiophen-4-one A 500mL three neck flask was charged with 8 g of phosphorus pentoxide (57mmol) and 45 g of polyphosphoric acid (475 mmol). The system was fittedwith a mechanical stirred, capped with an addition funnel, condensor andsepta and purged with nitrogen. The system was heated to 150° C. untilnearly all the phsophorus pentoxide dissolved in the viscous mixture(about 1.5 hours). Once nearly all solid had dissolved, the system wascooled to 70° C. and over 3 hours a 350 mL dichloromethane solutioncontaining 8.3 g of 2-methyl-3-phenyl-thiophene (47.6 mmol) and 7 g ofmethacrylic acid (83 mmol) was added. After stirring for an additional 2hours, another 4 g of methacrylic acid (46 mmol) was added followed 2hours later by addition of another 4 g of methacyrlic acid (46 mmol).After stirring at 70° C. for 14 hrs, the mixture was cooled to 0° C. and100 mL of ice water was added. After stirring for 1 hour, the organiclayer was separated and the aqueous phase extracted twice with 75 mL ofdichloromethane. The organic extracts were combined, concentrated andwashed three times with 1.0 M NaOH solution The organic extracts werethen dried over magnesium sulfate, filtered and the volatiles removed byrotary evaporation to leave 10.3 g of oil (89 percent).

¹H NMR (CD₂Cl₂): 7.5-7.3 (m, 5H), 3.2 (d, 1H), 2.85 (d, 1H), 2.6-2.5 (m,4H), 1.35-1.25 (d, 3H).

5,6-Dihydro-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thiophene-4-ol A 500mL flask was charged with 9.9 g (41 mmol) of5,6-dihydro-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thiophen-4-onefollowed by 200 mL of THF. After sparging with nitrogen and cooling to0° C., a 20 mL 1.0 M solution of lithium aluminum hydride in ether (20.4mmol) was added over 20 minutes. After the addition was complete, thereaction was allowed to warm to room temperature and stirred for 1.5hours. The mixture was quenched with 200 mL of water and 150 mL of etherwere added. The mixture was filtered to remove the solids and theorganic layer was separated. The water layer was washed twice with 100mL of ether and the extracts combined and dried over magnesium sulfate.The mixture was filtered and the volatiles removed by rotary evaporationto leave 10.3 g of oil (104 percent).

¹H NMR (CD₂Cl₂): 7.8-7.2 (m, 5H), 4.95 (d, 0.4H), 4.82 (d, 0.6H),3.1-2.6 (m, 4H), 2.6-2.2 (m, 3H), 1.2-1.35 (m, 3H). ¹³C{¹H} NMR(CD₂Cl₂): 148.40, 146.66, 140.6, 139.70, 139.30, 136.20, 134.05, 129.08,128.56, 126.91, 80.70, 74.24, 48.88, 43.77, 35.59, 35.37, 19.2, 15.13,14.54.

2,5-dimethyl-3-phenyl-6H-cyclopenta[b]thiophene A 250 mL flask wascharged 9.1 g (37 mmol) of5,6-Dihydro-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thiophene-4-olfollowed by 175 mg (0.9 mmol) of p-toluenesulfonic acid and 50 mL ofbenzene. The mixture was sparged with nitrogen and heated to 45° C. for15 min—the reaction was then cooled and quenched by adding 150 mL of aice cold saturated water/sodium bicarbonate mixture. The organic layerwas separated, the extract dried over magnesium sulfate, filtered andthe volatiles removed in vacuo. The compound was dissolved in hexanesand purified by column chromatography to give 4.2 g of the desiredmaterial (50 percent).

¹H NMR (CD₂Cl₂): 7.55-7.25 (m, 5H), 6.44/6.35 (2 s, 1H), 3.14 (s, 2H),2.5 (m, 3H), 2.15 (s, 3H). ¹³C{¹H} NMR (CD₂Cl₂): 145.72, 145.65, 140.72,136.76, 133.42, 129.22, 128.85, 126.92, 126.76, 122.08, 121.79, 40.61,16.88, 14.84, 14.18.

2,5-dimethyl-3-phenyl-cyclopenta[b]thiophene(-1)lithium A 125 mL jar wascharged with 3.29 g (14.5 mmol) of2,5-dimethyl-3-phenyl-6H-cyclopenta[b]thiophene and 75 mL of hexanes. Tothis was added over five minutes 9.7 mL of nBuLi in hexanes (15.3 mmol,1.6 M). The mixture was stirred at room temperature for several days andthe obtained precipitate was filtered and washed twice with 25 mL ofhexanes. The solid was dried in vacuo for two hours to leave 3.1 ofsolid (92 percent).

N-(1,1-dimethylethyl)-1-(2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-4-yl)-1,1-dimethylsilanamineA 125 mL flask was charged with 1.12 g (4.8 mmol) of2,5-dimethyl-3-phenyl-cyclopenta[b]thiophene(1)lithium and to this added25 mL of THF. To this solution was added a 5 mL THF solution containing0.95 g (5.8 mmol) ofN-(tert-butyl)-1,1-dimethyl-1-(chloromethyl)silanamine. The mixture wasstirred at room temperature for 3 hours and the volatiles removed invacuo. The residue was extracted into 40 mL of hexanes, filtered and thevolatiles removed in vacuo to leave 1.62 g of yellow oil, 94 percent.

¹H NMR (C₆D₆): 7.47 (d, 2H), 7.26-7.1 (m, 3H), 6.52 (s, 1H), 3.29 (s,1H), 2.37 (s, 3H), 2.09 (s, 3H), 1.10 (s, 9H), 0.09 (s, 3H), 0.04 (s,3H). ¹³C{¹H} NMR (C₆D₆): 149.00, 146.59, 137.67, 137.23, 134.87, 129.55,128.55, 126.54, 122.48, 50.86, 33.69, 18.04, 14.69, −0.61, −1.56.

[1-[(3a,4,5,6,6a-η)-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]bis(N,N-dimethylaminotitanium) A 90 mL flask was charged with 1.51 g ofN-(1,1-dimethylethyl)-1-(2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-4-yl)-1,1-dimethylsilanamine,990 mg of Ti(NMe₂)₄ and 40 mL of octane. The mixture was heated toreflux for 11 hrs at which time there was nearly complete conversion ofthe starting material to the crude diamide complex.

¹HNMR (C₆D₆): 7.40 (d, 2H), 7.27 (t, 2H), 7.10 (m, 1H), 2.97 (s, 6H,NMe₂), 2.72 (s, 6H, NMe₂), 5.93 (s, 1H), 2.12 (s, 3H), 2.08 (s, 3H),1.30 (s, 9H), 0.77 (s, 3H), 0.58 (s, 3H).

Example 4

[1-[(3a,4,5,6,6a-η)-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dichlorotitanium)

The reaction mixture of example 3 was diluted with 20 mL of toluene andto this added 15 mL of chlorotrimethylsilane. After 6 hours, thevolatiles were removed in vacuo and the residue extracted into toluene,filtered and the volatiles removed in vacuo. To the residue was added 10mL of hexanes and after stirring for 10 minutes, the suspension wasconcentrated to about 6 mL and cooled to −30° C. overnight. The motherliquor was decanted, the solid washed twice with 5 mL of cold hexanesand the solid dried in vacuo (1^(st) crop: 220 mg). The hexanes motherliquor was concentrated to about 3 mL and cooled to −30° C. to give asecond crop of 680 mg of material. The hexanes mother liquor wasconcentrated to dryness and the residue triturated with 3 mL of hexanesand the suspension cooled to −30° C. to give a 3rd crop of 140 mg. TheNMR spectra of all three crops are essentially identical: total yield1.04 g, 51 percent

¹H NMR (C₆D₆): 7.49 (d, 2H), 7.24-7.15 (m, 3H), 6.59 (s, 1H), 2.13 (s,3H), 2.07 (s, 3H), 1.39 (s, 9H), 0.63 (s, 3H), 0.40 (s, 3H). ¹³C{¹H} NMR(C₆D₆): 147.06, 146.68, 144.97, 139.66, 134.51, 130.45, 129.89, 129.14,128.80, 117.65, 117.36, 62.01, 32.33, 19.79, 15.11, 3.40, 3.18.

Example 5

[1-[(3a,4,5,6,6a-η)-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dimethyltitanium) A 90 mL jar was charged with 0.14 g (0.30 mmol) of[1-[(3a,4,5,6,6a-η)-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]bis(N,N-dichlorotitanium). To this was added 20 mL of ether and the solution cooled to−30° C. To this was added 0.3 mL (0.9 mmol, 3.0 M) of methyl magnesiumbromide and after 40 minutes, the volatiles were removed and thematerial extracted into 20 mL of hexanes. After 10 minutes of stirring,the suspension was filtered and the filtrate concentrated to dryness.The solid was again extracted into 10 mL of hexanes, filtered and thefiltrate concentrated to dryness to leave 118 mg (0.30 mmol, 92 percent)of yellow solid.

¹H NMR (C₆D₆): 7.47 (d, 2H), 7.25 (t, 2H), 7.13 (m, 1H), 6.72 (s, 1H),2.19 (s, 3), 1.92 (s, 3), 1.54 (s, 9H), 0.79 (s, 3H), 0.57 (s, 3H), 0.42(s, 31), 0.39 (s, 3H). ¹³C{¹H} NMR (C₆D₆): 141.97, 141.04, 139.56,135.78, 135.64, 129.97, 128.91, 128.88, 112.94, 57.74, 57.05, 50.93,34.36, 18.39, 14.89, 4.36, 4.01.

Polymerization General Conditions

Mixed alkanes and liquid olefins are purified by sparging with purifiednitrogen followed by passage through columns containing alumina (A-2,available from LaRoche Inc.) and Q5 reactant (available from EnglehardChemicals Inc.) at 50 psig (450 kPa) using a purified nitrogen pad. Alltransfers of solvents and solutions described below are accomplishedusing a gaseous pad of dry, purified nitrogen or argon. Gaseous feeds tothe reactor are purified by passage through columns of A-204 alumina(available from LaRoche Inc.) and Q5 reactant. The aluminas arepreviously activated by treatment at 375° C. with nitrogen, and Q5reactant is activated by treatment at 200° C. with 5 percent hydrogen innitrogen.

Polymerization 1

A stirred, two-liter Parr reactor was charged with 740 g of mixedalkanes (Isopar E™) and with 118 g of purified 1-octene comonomer.Hydrogen (25 psi (170 kPa), 5.7 mmoles) was added as a molecular weightcontrol agent by differential pressure expansion from a 75 mL additiontank at 300 psig (2.2 MPa). The reactor was heated to 140° C. andsaturated with ethylene at 500 psig (3.5 MPa). Catalyst andmethyldi(C₁₄₋₁₈ alkyl)ammonium tetrakis(pentafluorophenyl)borate (MDPB)or trispentafluorophenylborane (FAB) cocatalyst as 0.005M solutions intoluene were premixed in a glovebox and transferred to a catalystaddition tank and injected into the reactor. The polymerizationconditions were maintained during the run with ethylene on demand.

After 15 minute reaction time, the resulting solution was removed fromthe reactor into a nitrogen purged collection vessel containing 100 mlof isopropyl alcohol and 20 ml of a 10 weight percent toluene solutionof hindered phenol antioxidant (Irganox™ 1010 from Ciba GeigyCorporation) and phosphorus stabilizer (Irgafos™ 168 from Ciba GeigyCorporation). Polymers formed are dried in a programmed vacuum oven witha maximum temperature of 145° C. and a 20 hour heating period. Theresults are contained in Table 1. TABLE 1 Catalyst Cocatalyst YieldEfficiency Density Run μmoles μmoles (g) (g/μg Ti) g/ml MMI² Mw MWD  1*ID¹ (0.3) MDPB (0.3) 75.1 5.23 0.881 0.8 144,000 2.1  2 Ex. 2(0.3) ″76.8 5.35 0.885 2.2  3 Ex. 2(0.3) ″ 83.6 5.82 0.884 3.0 81,900 3.1  4Ex. 5(0.3) ″ 96.3 6.70 0.877 4.2  5 Ex. 5(0.3) ″ 91.8 6.40 0.877 4.083,000 2.6  6* ID¹ (0.9) FAB (0.9) 58.9 1.37 0.885 0.4 130,000 2.7  7Ex. 2 (0.8) FAB (0.8) 74.9 1.96 0.886 3.0  8 Ex. 2 (0.8) ″ 79.3 2.070.885 3.4 85,200 3.4  9 Ex. 5 (1.5) FAB (1.5) 82.6 1.15 0.876 2.3 10 Ex.5 (1.5) ″ 76.4 1.06 0.875 2.4 92,600 2.4*comparative, not an example of the invention¹(dimethyl(N-tert-butyl)-1,1-dimethyl-1-((1,2,3,3a,8a-η)-1,5,6,7-tetrahydro-2-methyl-s-indacen-1-yl)-silananiinato(2-)-κN)-titanium)prepared as outlined in WO98/27103²melt index as determined by micromelt technique

1. A polycyclic, heteroatom containing fused ring compound correspondingto the formula: CpM(Z)(X)_(x)(T)_(t)(X′)_(x′)(I), where Cp is apolycyclic, fused ring ligand or inertly substituted derivative thereofhaving up to 60 atoms not counting hydrogen, said Cp comprising at leasta cyclopentadienyl ring bound to M by means of delocalized π-electronsand having fused thereto a 5-membered polyatomic ring containing one ormore ring atoms selected from groups 15 or 16 of the Periodic Table ofthe Elements, or substituted derivatives thereof, with the proviso thatsaid cyclopentadienyl ring lacks adjacent substituents that togetherform a second fused ring; M is a metal selected from Groups 3-10 or theLanthanide series of the Periodic Table of the Elements; Z is a divalentmoiety of the formula -Z′Y— joining Cp and M, wherein, Z′ is SiR⁶ ₂, CR⁶₂, SiR⁶ ₂SiR⁶ ₂, CR⁶ ₂CR⁶ ₂, CR⁶═CR⁶, CR⁶ ₂SiR⁶ ₂, BR⁶, or GeR⁶ ₂; Y is—O—, —S—, —NR⁵—, —PR⁵—; —NR⁵ ₂, or —PR⁵ ₂; R⁵, independently eachoccurrence, is hydrocarbyl, trihydrocarbylsilyl, ortrihydrocarbylsilylhydrocarbyl, said R⁵ having up to 20 atoms other thanhydrogen, and optionally two R⁵ groups or R⁵ together with Y form a ringsystem; R⁶, independently each occurrence, is hydrogen, or a memberselected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl,halogenated aryl, —NR⁵ ₂, and combinations thereof, said R⁶ having up to30 non-hydrogen atoms, and optionally, two R⁶ groups form a ring system;X is hydrogen or a monovalent anionic ligand group having up to 60 atomsnot counting hydrogen; T independently each occurrence is a neutralligating compound having up to 20 atoms, other than hydrogen, andoptionally T and X or T and R⁵ are bonded together; X′ is a divalentanionic ligand group having up to 60 atoms other than hydrogen; x is 0,1, 2, or 3; t is a number from 0 to 2, and x′ is 0 or
 1. 2. A compoundaccording to claim 1 corresponding to the formula:

wherein: J independently each occurrence is hydrogen, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylgermyl, halide, hydrocarbyloxy,trihydrocarbylsiloxy, bis(trihydrocarbylsilyl)amino,di(hydrocarbyl)amino, hydrocarbyleneamino, hydrocarbylimino,di(hydrocarbyl)phosphino, hydrocarbylenephosphino, hydrocarbylsulfido,halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,trihydrocarbylsilyl-substituted hydrocarbyl,trihydrocarbylsiloxy-substituted hydrocarbyl,bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said J group having up to 40atoms not counting hydrogen atoms; A is the divalent remnant of a5-membered, aromatic ring group or a substituted derivative thereof,said A containing at least one Group 15 or 16 ring atom; and M is aGroup 4 metal; Y is —O—, —S—, —NR⁵—, —PR⁵—; —NR⁵ ₂, or —PR⁵ ₂; Z′ isSiR⁶ ₂, CR⁶ ₂, SiR⁶ ₂SiR⁶ ₂, CR⁶ ₂CR⁶ ₂, CR⁶═CR⁶, CR⁶ ₂SiR⁶ ₂, BR⁶, orGeR⁶ ₂; R⁵ each occurrence is independently hydrocarbyl,trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl, said R⁵ havingup to 20 atoms other than hydrogen, and optionally two R⁵ groups or R⁵together with Y form a ring system; R⁶ each occurrence is independentlyhydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl,halogenated alkyl, halogenated aryl, —NR⁵ ₂, and combinations thereof,said R⁶ having up to 20 non-hydrogen atoms, and optionally, two R⁶groups form a ring system; X, T, and X′ are as previously defined inclaim 1; x is 0, 1 or 2; t is 0 or 1; and x′ is 0 or
 1. 3. A metalcomplex according to claim 1, corresponding to the formula:

wherein M is titanium; R¹ each occurrence is hydrogen or a hydrocarbyl,hydrocarbyloxy, dihydrocarbylamino, hydrocarbyleneamino,dihydrocarbylamino-substituted hydrocarbyl group, orhydrocarbyleneamino-substituted hydrocarbyl group of up to 30 atoms notcounting hydrogen; Y is —O—, —S—, —NR⁵—, —PR⁵—; —NR⁵ ₂, or —PR⁵ ₂; Z′ isSiR⁶ ₂, CR⁶ ₂, SiR⁶ ₂SiR⁶ ₂, CR⁶ ₂CR⁶ ₂, CR⁶═CR⁶, CR⁶ ₂SiR⁶ ₂, BR⁶, orGeR⁶ ₂; R⁵ each occurrence is independently hydrocarbyl,trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl, said R⁵ havingup to 20 atoms other than hydrogen, and optionally two R⁵ groups or R⁵together with Y form a ring system; R⁶ each occurrence is independentlyhydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl,halogenated alkyl, halogenated aryl, —NR⁵ ₂, and combinations thereof,said R⁶ having up to 20 non-hydrogen atoms, and optionally, two R⁶groups form a ring system; X, T, and X′ are as previously defined inclaim 1; x is 0, 1 or 2; t is 0 or 1; and x′ is 0 or 1; and, when x is2, x′ is zero, M is in the +4 formal oxidation state (or M is in the +3formal oxidation state if Y is —NR⁵ ₂ or —PR⁵ ₂), and X is an anionicligand selected from the group consisting of halide, hydrocarbyl,hydrocarbyloxy, di(hydrocarbyl)amido, di(hydrocarbyl)phosphido,hydrocarbylsulfido, and silyl groups, as well as halo-,di(hydrocarbyl)amino-, hydrocarbyloxy-, anddi(hydrocarbyl)phosphino-substituted derivatives thereof, said X grouphaving up to 30 atoms not counting hydrogen, when x is 0 and x′ is 1, Mis in the +4 formal oxidation state, and X′ is a dianionic ligandselected from the group consisting of hydrocarbadiyl, silane,oxyhydrocarbylene, and hydrocarbylenedioxy groups, said X group havingup to 30 nonhydrogen atoms, when x is 1, and x′ is 0, M is in the +3formal oxidation state, and X is a stabilizing anionic ligand groupselected from the group consisting of allyl,2-(N,N-dimethylamino)phenyl, 2-(N,N-dimethylaminomethyl)phenyl, and2-(N,N-dimethylamino)benzyl, and when x and x′ are both 0, t is 1, M isin the +2 formal oxidation state, and T is a neutral, conjugated ornonconjugated diene, optionally substituted with one or more hydrocarbylgroups, said L having up to 40 carbon atoms and being bound to M bymeans of delocalized π-electrons thereof.
 4. A metal complex accordingto claim 1 selected from the group consisting of:[1-[(3a,4,5,6,6a-η)-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dichloro titanium),[1-[(3a,4,5,6,6a-η)-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dimethyl titanium),[1-[(3a,4,5,6,6a-η)-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dibenzyl titanium),[1-[(3a,4,5,6,6a-η)-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (II) 1,3-pentadiene),[1-[(3a,4,5,6,6a-η)-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (II) 1,4-diphenyl-1,3-butadiene,[1-[(3a,4,5,6,6a-η)-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium (III) 2-(N,N-dimethylamino)benzyl),[1-[(3a,4,5,6,6a-η)-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dichlorotitanium),[1-[(3a,4,5,6,6a-η)-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dimethyltitanium),[1-[(3a,4,5,6,6a-η)-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dibenzyltitanium),[1-[(3a,4,5,6,6a-η)-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(II) 1,3-pentadiene),[1-[(3a,4,5,6,6a-η)-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(II) 1,4-diphenyl-1,3-butadiene,[1-[(3a,4,5,6,6a-η)-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(III) 2-(N,N-dimethylamino)benzyl),[1-[(3a,4,5,6,6a-η)-3-phenyl-5-methyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dichlorotitanium),[1-[(3a,4,5,6,6a-η)-3-phenyl-5-methyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dimethyltitanium),[1-[(3a,4,5,6,6a-η)-3-phenyl-5-methyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dibenzyltitanium),[1-[(3a,4,5,6,6a-η)-3-phenyl-5-methyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(II) 1,3-pentadiene),[1-[(3a,4,5,6,6a-η)-3-phenyl-5-methyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(II) 1,4-diphenyl-1,3-butadiene,[1-[(3a,4,5,6,6a-η)-3-phenyl-5-methyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(III) 2-(N,N-dimethylamino)benzyl),[1-[(3a,4,5,6,6a-η)-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dichlorotitanium),[1-[(3a,4,5,6,6a-η)-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dimethyltitanium),[1-[(3a,4,5,6,6a-η)-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dibenzyltitanium),[1-[(3a,4,5,6,6a-η)-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(II) 1,3-pentadiene),[1-[(3a,4,5,6,6a-η)-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(II) 1,4-diphenyl-1,3-butadiene,[1-[(3a,4,5,6,6a-η)-2,5-dimethyl-3-phenyl-4H-cyclopenta[b]thien-6-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(III) 2-(N,N-dimethylamino)benzyl),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-cyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dichlorotitanium),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-cyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dimethyltitanium),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-cyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dibenzyltitanium),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-cyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(II) 1,3-pentadiene),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-cyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium.(II) 1,4-diphenyl-1,3-butadiene,[1-[(3a,4,5,6,6a-η)-1,4-dihydro-cyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(III) 2-(N,N-dimethylamino)benzyl),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dichlorotitanium),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dimethyltitanium),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dibenzyltitanium),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(II) 1,3-pentadiene),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(II) 1,4-diphenyl-1,3-butadiene,[1-[(3a,4,5,6,6a-η)-1,4-dihydro-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(III) 2-(N,N-dimethylamino)benzyl),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dichlorotitanium),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dimethyltitanium),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dibenzyltitanium),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(II) 1,3-pentadiene),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(II) 1,4-diphenyl-1,3-butadiene,[1-[(3a,4,5,6,6a-η)-1,4-dihydro-5-methyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(III) 2-(N,N-dimethylamino)benzyl),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-2,5-dimethyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dichlorotitanium),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-2,5-dimethyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dimethyltitanium),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-2,5-dimethyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-1,1dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]dibenzyltitanium),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-2,5-dimethyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(II) 1,3-pentadiene),[1-[(3a,4,5,6,6a-η)-1,4-dihydro-2,5-dimethyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(II) 1,4-diphenyl-1,3-butadiene,[1-[(3a,4,5,6,6a-η)-1,4-dihydro-2,5-dimethyl-1-phenylcyclopenta[b]pyrrol-4-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamato(2-)-κN]titanium(III) 2-(N,N-dimethylamino)benzyl), and mixtures thereof.
 5. An olefinpolymerization process comprising contacting one or more olefin monomersunder polymerization conditions with a catalyst composition comprising ametal complex according to any one of claims 1-4.
 6. The process ofclaim 5 wherein the catalyst composition additionally comprises anactivating cocatalyst.
 7. The process of claim 5 conducted undersolution, slurry or high pressure polymerization conditions.
 8. Theprocess of claim 5 conducted under slurry or gas phase polymerizationconditions, wherein the catalyst additionally comprises an inert,particulated support.
 9. The process of claim 6 wherein the activatingcocatalyst is: trispentafluorophenylborane, methylditetradecylammoniumtetrakis(pentafluorophenyl)borate,(pentafluorophenyl)ditetradecylammoniumtetrakis(pentafluorophenyl)borate, dimethyltetradecylammoniumtetrakis(pentafluorophenyl)borate, methyldihexadecylammoniumtetrakis(pentafluorophenyl)borate,(pentafluorophenyl)dihexadecylammoniumtetrakis(pentafluorophenyl)borate, dimethylhexadecylammoniumtetrakis(pentafluorophenyl)borate, methyldioctadecylammoniumtetrakis(pentafluorophenyl)borate,(pentafluorophenyl)dioctadecylammonium tetrakispentafluorophenyl)borate, dimethyloctadecylammoniumtetrakis(pentafluorophenyl)borate, methylalumoxane, triisobutylaluminummodified methylalumoxane, or a mixture thereof.